High‐Performance Bismuth‐Doped Nickel Aerogel Electrocatalyst for the Methanol Oxidation Reaction

Low‐cost, non‐noble‐metal electrocatalysts are required for direct methanol fuel cells, but their development has been hindered by limited activity, high onset potential, low conductivity, and poor durability. A surface electronic structure tuning strategy is presented, which involves doping of a foreign oxophilic post‐transition metal onto transition metal aerogels to achieve a non‐noble‐metal aerogel Ni₉₇Bi₃ with unprecedented electrocatalytic activity and durability in methanol oxidation. Trace amounts of Bi are atomically dispersed on the surface of the Ni₉₇Bi₃ aerogel, which leads to an optimum shift of the d‐band center of Ni, large compressive strain of Bi, and greatly increased conductivity of the aerogel. The electrocatalyst is endowed with abundant active sites, efficient electron and mass transfer, resistance to CO poisoning, and outstanding performance in methanol oxidation. This work sheds light on the design of high‐performance non‐noble‐metal electrocatalysts.     

Crystal‐Phase‐Engineered PdCu Electrocatalyst for Enhanced Ammonia Synthesis

Crystal phase engineering is a powerful strategy for regulating the performance of electrocatalysts towards many electrocatalytic reactions, while its impact on the nitrogen electroreduction has been largely unexplored. Herein, we demonstrate that structurally ordered body‐centered cubic (BCC) PdCu nanoparticles can be adopted as active, selective, and stable electrocatalysts for ammonia synthesis. Specifically, the BCC PdCu exhibits excellent activity with a high NH₃ yield of 35.7 μg h^?1 mg^?1_cat, Faradaic efficiency of 11.5 %, and high selectivity (no N₂H₄ is detected) at ?0.1 V versus reversible hydrogen electrode, outperforming its counterpart, face‐centered cubic (FCC) PdCu, and most reported nitrogen reduction reaction (NRR) electrocatalysts. It also exhibits durable stability for consecutive electrolysis for five cycles. Density functional theory calculation reveals that strong orbital interactions between Pd and neighboring Cu sites in BCC PdCu obtained by structure engineering induces an evident correlation effect for boosting up the Pd 4d electronic activities for efficient NRR catalysis. Our findings open up a new avenue for designing active and stable electrocatalysts towards NRR.     

A Facile Strategy to PdCu Bimetallic Alloy Nanosponges with Highly Porous Features as a High‐Performance Electrocatalytic Activity for Ethanol Electrooxidation in an Alkaline Medium

Well‐defined three‐dimensional (3D) PdCu bimetallic alloy nanosponges (BANs) with highly porous structure was reported through a rapid and general strategy. Significantly, the as‐prepared PdCu BANs exhibited greatly enhanced activity and stability than commercial Pd/C catalyst towards ethanol electrooxidation in an alkaline medium. Pd₁Cu₁ shows higher active area and better electrocatalytic activity than Pd₁Cu₂ and Pd₂Cu₁. This result demonstrates the potential of applying these PdCu BANs as effective electrocatalysts for direct alcohol fuel cells (DAFCs).     

Ethylene Glycol Electrooxidation Based on Pentangle‐Like PtCu Nanocatalysts

The research of active and stable electrocatalysts toward liquid‐fuel oxidation reaction is of great significance for the large‐scale commercialization of fuel cells. Although extensive efforts have been devoted to pursuing high‐performance nanocatalysts for fuel cells, both the high cost and sluggish reaction kinetics have been two major drawbacks that limited its commercial development. In this regard, we demonstrated a facile solvothermal method for the syntheses of an advanced class of PtCu nanocatalysts with a unique pentangle‐like shape. By combining the merits of a highly active surface area as well as the synergistic and electronic effects, the as‐prepared pentangle‐like Pt₃Cu nanocatalysts showed superior electrocatalytic activity towards ethylene glycol oxidation with a mass and specific activities of 5162.6 mA mg^?1 and 9.7 mA cm^?2, approximately 5.0 and 5.1 times higher than the commercial Pt/C, respectively. More significantly, the Pt₃Cu pentangle also showed excellent long‐term stability with less activity decay and negligible changes in structure after 500 cycles, indicating another class of anode catalysts for fuel cells and beyond.     

High-Performance Bismuth-Doped Nickel Aerogel Electrocatalyst for the Methanol Oxidation Reaction

Low-cost, non-noble-metal electrocatalysts are required for direct methanol fuel cells, but their development has been hindered by limited activity, high onset potential, low conductivity, and poor durability. A surface electronic structure tuning strategy is presented, which involves doping of a foreign oxophilic post-transition metal onto transition metal aerogels to achieve a non-noble-metal aerogel Ni₉₇Bi₃ with unprecedented electrocatalytic activity and durability in methanol oxidation. Trace amounts of Bi are atomically dispersed on the surface of the Ni₉₇Bi₃ aerogel, which leads to an optimum shift of the d-band center of Ni, large compressive strain of Bi, and greatly increased conductivity of the aerogel. The electrocatalyst is endowed with abundant active sites, efficient electron and mass transfer, resistance to CO poisoning, and outstanding performance in methanol oxidation. This work sheds light on the design of high-performance non-noble-metal electrocatalysts.     

Crystal-Phase-Engineered PdCu Electrocatalyst for Enhanced Ammonia Synthesis

Crystal phase engineering is a powerful strategy for regulating the performance of electrocatalysts towards many electrocatalytic reactions, while its impact on the nitrogen electroreduction has been largely unexplored. Herein, we demonstrate that structurally ordered body-centered cubic (BCC) PdCu nanoparticles can be adopted as active, selective, and stable electrocatalysts for ammonia synthesis. Specifically, the BCC PdCu exhibits excellent activity with a high NH₃ yield of 35.7 μg h⁻¹ mg⁻¹_cat, Faradaic efficiency of 11.5 %, and high selectivity (no N₂H₄ is detected) at −0.1 V versus reversible hydrogen electrode, outperforming its counterpart, face-centered cubic (FCC) PdCu, and most reported nitrogen reduction reaction (NRR) electrocatalysts. It also exhibits durable stability for consecutive electrolysis for five cycles. Density functional theory calculation reveals that strong orbital interactions between Pd and neighboring Cu sites in BCC PdCu obtained by structure engineering induces an evident correlation effect for boosting up the Pd 4d electronic activities for efficient NRR catalysis. Our findings open up a new avenue for designing active and stable electrocatalysts towards NRR.     

Influence of Metal Oxides on Platinum Activity towards Methanol Oxidation in H2SO4 solution

Pt–CeO₂/C, Pt–TiO₂/C, and Pt–ZrO₂/C electrocatalysts were prepared by using a modified microwave‐assisted polyol process. Physical characterization was performed by using XRD, TEM, and EDX analyses. The incorporation of different metal oxides increased the dispersion degree of Pt nanoparticles and reduced their diameter to 2.50 and 2.33 nm when TiO₂ and ZrO₂ were introduced to Pt/C, respectively. The electrocatalytic activity of various electrocatalysts was examined towards methanol oxidation in H₂SO₄ solution by using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. Among the studied composites, Pt–ZrO₂/C was selected to be a candidate electrocatalyst for better electrochemical performance in direct methanol fuel cells.     

Research advances in unsupported Pt-based catalysts for electrochemical methanol oxidation

Direct methanol fuel cells are one of the most promising alternative energy technologies in the foreseeable future, but its successful commercialization in large scale is still heavily hindered by several technical shortfalls, especially the undesirable activity and durability issues of electrocatalysts toward methanol oxidation reaction. In light of these challenges, the inherent advantages of unsupported Pt based nanostructures demonstrate their great potentials as durable and efficient electrocatalysts for direct methanol fuel cells. This review will summarize recent achievements of unsupported Pt-based electrocatalysts toward methanol oxidation, with highlighting the interactions between the performance and structure tailoring and composition modulating. At last, a perspective is proposed for the upcoming challenges and possible opportunities to further prompt the practical application of unsupported Pt-based electrocatalysts for direct methanol fuel cells.     

Hollow PtPd Nanorods with Mesoporous Shells as an Efficient Electrocatalyst for the Methanol‐Oxidation Reaction

Tailoring the morphology and composition of platinum‐based electrocatalysts is of significant importance for the development of highly efficient direct methanol fuel cells. Herein, we report a dual‐templating method for the design of hollow PtPd nanorods with mesoporous shells (mPtPd HNRs). We found that F127 micelles favored the formation of mesoporous structures and that SiO₂ nanorods served as a hard template for the creation of cavities. The well‐developed mesopores, hollow structures, and bimetallic composition of the mPtPd HNRs afforded a sufficient number of active sites to facilitate the electrochemical oxidation of methanol, thereby leading to enhanced activity and stability. This strategy allowed for the reliable preparation of mesoporous hollow platinum‐based electrocatalysts with desired compositions and morphologies for catalytic applications.     

Accelerating Oxygen‐Reduction Catalysts through Preventing Poisoning with Non‐Reactive Species by Using Hydrophobic Ionic Liquids

Developing cost‐effective electrocatalysts for the oxygen reduction reaction (ORR) is a prerequisite for broad market penetration of low‐temperature fuel cells. A major barrier stems from the poisoning of surface sites by nonreactive oxygenated species and the sluggish ORR kinetics on the Pt catalysts. Herein we report a facile approach to accelerating ORR kinetics by using a hydrophobic ionic liquid (IL), which protects Pt sites from surface oxidation, making the IL‐modified Pt intrinsically more active than its unmodified counterpart. The mass activity of the catalyst is increased by three times to 1.01 A mg^?1_Pt@0.9 V, representing a new record for pure Pt catalysts. The enhanced performance of the IL‐modified catalyst can be stabilized after 30 000 cycles. We anticipate these results will form the basis for an unprecedented perspective in the development of high‐performing electrocatalysts for fuel‐cell applications.     

Noble‐Metal Nanocrystals with Controlled Facets for Electrocatalysis

Noble‐metal nanocrystals (NCs) show excellent catalytic performance for many important electrocatalysis reactions. The crystallographic properties of the facets by which the NCs are bound, closely associated with the shape of the NCs, have a profound influence on the electrocatalytic function of the NCs. To develop an efficient strategy for the synthesis of NCs with controlled facets as well as compositions, understanding of the growth mechanism of the NCs and their interaction with the chemical species involved in NC synthesis is quite important. Furthermore, understanding the facet‐dependent catalytic properties of noble‐metal NCs and the corresponding mechanisms for various electrocatalysis reactions will allow for the rational design of robust electrocatalysts. In this review, we summarize recently developed synthesis strategies for the preparation of mono‐ and bimetallic noble‐metal NCs by classifying them by the type of facets through which they are enclosed and discuss the electrocatalytic applications of noble‐metal NCs with controlled facets, especially for reactions associated with fuel‐cell applications, such as the oxygen reduction reaction and fuel (methanol, ethanol, and formic acid) oxidation reactions.     

Polyaniline‐Modified Silver and Binary Silver‐Cobalt Catalysts for Oxygen Reduction Reaction

Novel dendrite‐like silver particles were electrodeposited on Ti substrates from a supporting electrolyte‐free 30 mmol L^?1 Ag(NH₃)₂⁺ solution, to synthesize the den‐Ag/Ti electrode. Binary Ag_xCo_y/Ti electrodes with different Ag:Co atomic ratios were further obtained by electrodeposition of Co particles on the den‐Ag/Ti electrode. Polyaniline (PANI) modified den‐Ag/Ti and Ag_xCo_y/Ti electrodes, PANI(n)‐den‐Ag/Ti and PANI(n)‐Ag_xCo_y/Ti, were also obtained by cyclic voltammetry at different numbers of cycles (n) in acidic and alkaline solutions containing aniline, respectively. All these electrodes exhibit high electroactivity for oxygen reduction reaction (ORR) in alkaline solution and their electroactivities follow the order: PANI(15)‐Ag₃₁Co₆₉/Ti>Ag₃₁Co₆₉/Ti>PANI(20)‐den‐Ag/Ti>den‐Ag/Ti. Among them, PANI(15)‐Ag₃₁Co₆₉/Ti displays the highest electrocatalytic activity for ORR with a much positive onset potential of 0 V (vs. Ag/AgCl) and a high ORR current density of 1.2 mA cm^?2 at ?0.12 V (vs. Ag/AgCl). The electrocatalysts are electrochemically insensitive to methanol and ethanol oxidation, and, as cathode electrocatalysts of direct alcohol fuel cells, can resist poisoning by the possible alcohol crossover from the anode.     

Revealing the Effect of Surface Composition on Multiwalled Carbon Nanotubes Supported Pt-Fe Alloy Electrocatalysts for Methanol Oxidation Performance

The designs of efficient and inexpensive Pt-based catalysts for methanol oxidation reaction (MOR) are essential to boost the commercialization of direct methanol fuel cells. Here, the highly catalytic performance PtFe alloys supported on multiwalled carbon nanotubes (MWCNTs) decorating nitrogen-doped carbon (NC) have been successfully prepared via co-engineering of the surface composition and electronic structure. The Pt₁Fe₃@NC/MWCNTs catalyst with moderate Fe³⁺ feeding content (0.86 mA/mg_Pt) exhibits 2.26-fold enhancement in MOR mass activity compared to pristine Pt/C catalyst (0.38 mA/mg_Pt). Furthermore, the CO oxidation initial potential of Pt₁Fe₃@NC/MWCNTs catalyst is lower relative to Pt/C catalyst (0.71 V and 0.80 V). Benefited from the optimal surface compositions, the anti-corrosion ability of MWCNT, strong electron interaction between PtFe alloys and MWCNTs and the N-doped carbon (NC) layer, the Pt₁Fe₃@NC/MWCNTs catalyst presents an improved MOR performance and anti-CO poisoning ability. This study would open up new perspective for designing efficient electrocatalysts for the DMFCs field.     

Boosting Hydrogen Oxidation Activity of Ni in Alkaline Media through Oxygen‐Vacancy‐Rich CeO2/Ni Heterostructures

The search for highly efficient platinum group metal (PGM)‐free electrocatalysts for the hydrogen oxidation reaction (HOR) in alkaline electrolytes remains a great challenge in the development of alkaline exchange membrane fuel cells (AEMFCs). Here we report the synthesis of an oxygen‐vacancy‐rich CeO₂/Ni heterostructure and its remarkable HOR performance in alkaline media. Experimental results and density functional theory (DFT) calculations indicate the electron transfer between CeO₂ and Ni could lead to thermoneutral adsorption free energies of H* (ΔG_H*). This, together with the promoted OH* adsorption strength derived from the abundance of oxygen vacancies in the CeO₂ species, contributes to the excellent HOR performance with the exchange current density and mass activity of 0.038 mA cm_Ni^?2 and 12.28 mA mg_Ni^?1, respectively. This presents a new benchmark for PGM‐free alkaline HOR and opens a new avenue toward the rational design of high‐performance PGM‐free electrocatalysts for alkaline HOR.     

Bottom‐Up Fabrication of a Sandwich‐Like Carbon/Graphene Heterostructure with Built‐In FeNC Dopants as Non‐Noble Electrocatalyst for Oxygen Reduction Reaction

High‐performance non‐noble electrocatalysts for oxygen reduction reaction (ORR) are the prerequisite for large‐scale utilization of fuel cells. Herein, a type of sandwiched‐like non‐noble electrocatalyst with highly dispersed FeN_x active sites embedded in a hierarchically porous carbon/graphene heterostructure was fabricated using a bottom‐up strategy. The in situ ion substitution of Fe³⁺ in a nitrogen‐containing MOF (ZIF‐8) allows the Fe‐heteroatoms to be uniformly distributed in the MOF precursor, and the assembly of Fe‐doped ZIF‐8 nano‐crystals with graphene‐oxide and in situ reduction of graphene‐oxide afford a sandwiched‐like Fe‐doped ZIF‐8/graphene heterostructure. This type of heterostructure enables simultaneous optimization of FeN_x active sites, architecture and interface properties for obtaining an electron‐catalyst after a one‐step carbonization. The synergistic effect of these factors render the resulting catalysts with excellent ORR activities. The half‐wave potential of 0.88 V vs. RHE outperforms most of the none‐noble metal catalyst and is comparable with the commercial Pt/C (20 wt %) catalyst. Apart from the high activity, this catalyst exhibits excellent durability and good methanol‐tolerance. Detailed investigations demonstrate that a moderate content of Fe dopants can effectively increase the intrinsic activities, and the hybridization of graphene can enhance the reaction kinetics of ORR. The strategy proposed in this work gives an inspiration towards developing efficient noble‐metal‐free electrocatalysts for ORR.     

Titanium Dioxide‐Grafted Copper Complexes: High‐Performance Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Media

The sluggish kinetics of the oxygen reduction reaction (ORR) at the cathodes of fuel cells significantly hampers fuel cell performance. Therefore, the development of high‐performance, non‐precious‐metal catalysts as alternatives to noble metal Pt‐based ORR electrocatalysts is highly desirable for the large‐scale commercialization of fuel cells. TiO₂‐grafted copper complexes deposited on multiwalled carbon nanotubes (CNTs) form stable and efficient electrocatalysts for the ORR. The optimized catalyst composite CNTs@TiO₂–ZA–[Cu(phen)(BTC)] shows surprisingly high selectivity for the 4 e^? reduction of O₂ to water (approximately 97 %) in alkaline solution with an onset potential of 0.988 V vs. RHE, and demonstrates superior stability and excellent tolerance for the methanol crossover effect in comparison to a commercial Pt/C catalyst. The copper complexes were grafted onto the surface of TiO₂ through coordination of an imidazole‐containing ligand, zoledronic acid (ZA), which binds to TiO₂ through its bis‐phosphoric acid anchoring group. Rational optimization of the copper catalyst’s ORR performance was achieved by using an electron‐deficient ligand, 5‐nitro‐1,10‐phenanthroline (phen), and bridging benzene‐1,3,5‐tricarboxylate (BTC). This facile approach to the assembly of copper catalysts on TiO₂ with rationally tuned ORR activity will have significant implications for the development of high‐performance, non‐precious‐metal ORR catalysts.     

Methane activation at low temperature in an acidic electrolyte using PdAu/C,PdCu/C,and PdTiO2/C electrocatalysts for PEMFC

Pd/C, PdAu/C, PdCu/C, and PdTiO₂/C electrocatalysts were prepared by a sodium borohydride reduction process for methane activation at low temperatures in a PEMFC reactor. These electrocatalysts were characterized by XRD, TEM, XPS, ICP-MS, ATR-FTIR, and cyclic voltammetry. The diffractograms of Pd/C, PdAu(50:50)/C, PdCu(50:50)/C, and PdTiO₂(50:50)/C electrocatalysts showed peaks associated with Pd face-centered cubic structure. PdAu(50:50)/C showed a small shift in the peak center when it was compared to Pd/C, while PdCu(50:50)/C showed a shift to higher angles when it was also compared to Pd/C. This effect can be due to the formation of an alloy between Pd and Au, and Pd and Cu. By TEM experiments, a mean nanoparticle size was observed between 6.9 and 8.9 nm for all electrocatalysts. Cyclic voltammograms of Pd/C, PdAu/C, PdCu/C and PdTiO₂/C electrocatalysts showed an increase in current density values after the adsorption of methane The ATR-FTIR experiments showed for all electrocatalysts the formation of methanol and formic acidic. Polarization curves at 80 °C acquired in a PEMFC reactor showed that PdAu(50:50)/C and PdTiO₂(50:50)/C had superior performance when compared to Pd/C, indicating the beneficial effect of adding the co-catalyst; this behavior has been attributed to the bifunctional mechanism or electronic effect.

     

Electrocatalysts for methanol oxidation with ultra low content of Pt and Ru

We have developed efficient electrocatalysts for methanol oxidation using new synthetic method facilitating deposition of Pt–Ru very thin nanoplatelets on carbon nanoparticles The method involves oxidation of carbon support, adsorption of Pb²⁺, its reduction and galvanic displacement of Pb⁰ by Pt and/or Ru. The Pt mass activity of this catalyst is about 10 times higher than that of the commercial Pt–Ru/C. The catalyst with the 1:1 Pt/Ru ratio displayed the highest methanol oxidation activity per surface Pt atom. Our results demonstrate the new synthetic method that yields the catalyst with potential for solving the problem of high Pt loading in direct methanol fuel cell anodes.     

Ni3N as an Active Hydrogen Oxidation Reaction Catalyst in Alkaline Medium

Hydroxide‐exchange membrane fuel cells can potentially utilize platinum‐group‐metal (PGM)‐free electrocatalysts, offering cost and scalability advantages over more developed proton‐exchange membrane fuel cells. However, there is a lack of non‐precious electrocatalysts that are active and stable for the hydrogen oxidation reaction (HOR) relevant to hydroxide‐exchange membrane fuel cells. Here we report the discovery and development of Ni₃N as an active and robust HOR catalyst in alkaline medium. A supported version of the catalyst, Ni₃N/C, exhibits by far the highest mass activity and break‐down potential for a PGM‐free catalyst. The catalyst also exhibits Pt‐like activity for hydrogen evolution reaction (HER) in alkaline medium. Spectroscopy data reveal a downshift of the Ni d band going from Ni to Ni₃N and interfacial charge transfer from Ni₃N to the carbon support. These properties weaken the binding energy of hydrogen and oxygen species, resulting in remarkable HOR activity and stability.     

Completely Green Synthesis of Colloid Adams’ Catalyst α‐PtO2 Nanocrystals and Derivative Pt Nanocrystals with High Activity and Stability for Oxygen Reduction

We report a first solution strategy for controlled synthesis of Adams’ catalyst (i.e., α‐PtO₂) by a facile and totally green approach using H₂PtCl₆ and water as reactants. The prepared α‐PtO₂ nanocrystals (NCs) are ultrasmall in size and have very “clean” surfaces, which can be reduced to Pt NCs easily in ethanol under ambient conditions. Such Adams’ catalysts have been applied as electrocatalysts beyond the field of heterogeneous catalysis. Noticeably, the water‐only synthesized α‐PtO₂ NCs and their derivative Pt NCs all exhibit much higher oxygen reduction reaction (ORR) activities and stabilities than that of the state‐of‐art Pt/C electrocatalysts. This study provides an example on the organics‐free synthesis of α‐PtO₂ and Pt NCs as promising cathode catalysts for fuel cell applications and, particularly, this simple, straightforward method may open a new way for the synthesis of other “clean” functional nanomaterials.